CN109939734A - A kind of perfluorinated sulfonic resin catalyst, preparation method and preparing the application in Dichloromonofluoromethane - Google Patents
A kind of perfluorinated sulfonic resin catalyst, preparation method and preparing the application in Dichloromonofluoromethane Download PDFInfo
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- CN109939734A CN109939734A CN201910316238.8A CN201910316238A CN109939734A CN 109939734 A CN109939734 A CN 109939734A CN 201910316238 A CN201910316238 A CN 201910316238A CN 109939734 A CN109939734 A CN 109939734A
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- perfluorinated sulfonic
- sulfonic resin
- carrier
- catalyst
- dichloromonofluoromethane
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Abstract
The invention discloses a kind of perfluorinated sulfonic resin catalyst, the catalyst includes perfluorinated sulfonic resin and carrier, the carrier main carrier and secondary carrier, the main carrier is the bifluoride of alkali or alkaline earth metal, and the pair carrier is one or more of active carbon, graphite powder or land plaster；The weight ratio of the perfluorinated sulfonic resin, main carrier and secondary carrier is 1:1~3:1~3.Catalyst of the invention does not decompose under dry environment, is non-ignitable, can be used continuously.It is high to be used to prepare Dichloromonofluoromethane reaction conversion ratio, good, the no coupling product of selectivity, safe operation.
Description
Technical field
The present invention relates to a kind of catalyst, specially perfluorinated sulfonic resin catalyst, preparation methods, and are preparing two
Application in one fluoromethane of chlorine.
Background technique
Dichloromonofluoromethane, molecular formula CHCl2F, is generally called R21 or HFC-21, and English name is
Dichloromonofluoromethane, molecular weight 102.92,8.9 DEG C of boiling point, destroy ozone latent energy value by -135 DEG C of fusing point
(ODP) 0.01, global warming coefficient value (GWP) 0.05 is not soluble in water, is dissolved in ethyl alcohol.It is molten to be often used as solvent, refrigerant, gas
Glue stock solution etc..
The production technology of usual Dichloromonofluoromethane is under the catalytic action of Antimony pentachloride, and chloroform and hydrogen fluoride pass through
Fluorination reaction is made.Fluorinated hydrocarbons are prepared by chloralkane fluorination and are generally divided into liquid-phase fluorination process and gaseous fluoridizing method.
Liquid-phase fluorination process needs to add catalyst promoter when using antimony pentachloride catalyst, and process conditions are harsher, and equipment corrosion is tight
Weight, generates a large amount of three wastes.Gaseous fluoridizing method three-waste pollution is small, can be with continuous production.However, there remains Antimony pentachloride works
For catalyst, Antimony pentachloride also easily inactivates in catalytic process.Moreover, during generating Dichloromonofluoromethane very
It is easy to produce the serial by-product such as monochlorodifluoromethane (R22 or HFC-22) and fluoroform (R23 or HFC-23).
Perfluorinated sulfonic acid is a kind of super acids, due to introducing the maximum fluorine atom of electronegativity in molecule, generates powerful field effect
Should and inductive effect to make acid sharp increase be a kind of important catalyst in acidic catalyst reaction.Perfluorinated sulfonic resin be by
It carries out being copolymerized perfluorinated sulfonic resin obtained with sulfonic perfluorovinyl ether monomer and tetrafluoroethene, is that a kind of solid is super
Strong acid has the characteristics that good heat resistance, chemical stability and high mechanical strength.Compared with liquid superacid, it is used as catalyst
When, be easily isolated, can Reusability, it is small to equipment corrosion, selectivity it is good, environmental pollution is low, easy to industrialized production.Cause
This, exploitation prepare Dichloromonofluoromethane Dichloromonofluoromethane (R21 or HFC-21) catalyst and Dichloromonofluoromethane (R21 or
HFC-21) new preparation technology is also an innovative research.
Summary of the invention
The technical problem to be solved by the invention is to provide the preparations of a kind of new perfluorinated sulfonic resin and the catalyst
Method uses the catalyst preparation Dichloromonofluoromethane (R21 or HFC-21), no coupling product, safe operation.
In order to solve the above technical problems, the present invention discloses a kind of perfluorinated sulfonic resin catalyst first, the catalyst packet
Perfluorinated sulfonic resin and carrier, the carrier main carrier and secondary carrier are included, the main carrier is the fluorine of alkali or alkaline earth metal
Hydride, the pair carrier is one or more of active carbon, graphite powder or land plaster；The perfluorinated sulfonic resin,
The weight ratio of main carrier and secondary carrier is 1:1~3:1~3.Active carbon, graphite powder, land plaster as secondary carrier can be independent
It uses, can also be used in mixed way with arbitrary proportion.
The invention also discloses a kind of preparation methods of aforementioned perfluorinated sulfonic resin catalyst, by first by perfluorinated sulfonic acid tree
Rouge is dissolved in water and Isopropanol Solvent, and perfluorinated sulfonic resin catalyst then is made with main carrier, secondary carrier combination drying.
Further, the weight ratio of the component of the perfluorinated sulfonic resin, water and Isopropanol Solvent be 1:0.1~1:1~
1.5, solution temperature is 200~300 DEG C, and dissolution time is 1~5 hour.
Further, drying temperature is 150~200 DEG C, and drying time is 1~3 hour.
Aforementioned perfluorinated sulfonic resin catalyst is used to prepare in Dichloromonofluoromethane.
Further, the preparation method of Dichloromonofluoromethane is not: perfluorinated sulfonic resin catalyst is put into pipeline reactor
In, it is preheated after chloroform and hydrogen fluoride carried out at 250~350 DEG C continuity react be made Dichloromonofluoromethane, institute
The molar ratio for stating chloroform and hydrogen fluoride is 1:1~3.
Catalyst of the invention does not decompose under dry environment, is non-ignitable, can be used continuously.It is used to prepare one fluorine of dichloro
Methane reaction high conversion rate, good, the no coupling product of selectivity, safe operation.
Specific embodiment
Below with reference to embodiment, more specifically the elaboration contents of the present invention.Implementation of the invention is not limited to following reality
Example is applied, the accommodation in any form made to the present invention or changed all should be within the scope of the present invention.
The preparation of 1 catalyst 1 of embodiment
Perfluorinated sulfonic resin 100kg, deionized water 10kg, isopropanol 100kg are mixed, at 200 DEG C, after dissolution 5 hours,
Sodium bifluoride 100kg, active carbon 20kg, graphite powder 20kg is added, land plaster 60kg mixing is made at 200 DEG C and urges for dry 1 hour
Agent 1.
The preparation of 2 catalyst 2 of embodiment
Perfluorinated sulfonic resin 100kg, deionized water 100kg, isopropanol 150kg are mixed, at 300 DEG C, dissolved 1 hour
Afterwards, potassium bifluoride 100kg, active carbon 100kg mixing, in 150 DEG C of dry 3 hours obtained catalyst 2 is added.
The preparation of 3 catalyst 3 of embodiment
Perfluorinated sulfonic resin 100kg, deionized water 10kg, isopropanol 120kg are mixed, at 250 DEG C, after dissolution 3 hours,
Fluorine magnesium hydride 100kg, active carbon 50kg, land plaster 50kg mixing, in 150 DEG C of dry 3 hours obtained catalyst 3 is added.
The preparation of 4 catalyst 4 of embodiment
Perfluorinated sulfonic resin 100kg, deionized water 10kg, isopropanol 150kg are mixed, at 200 DEG C, after dissolution 2 hours,
Fluorine calcium hydride 100kg, graphite powder 100kg mixing, in 150 DEG C of dry 2 hours obtained catalyst 4 is added.
The preparation of 5 catalyst 5 of embodiment
Perfluorinated sulfonic resin 100kg, deionized water 50kg, isopropanol 100kg are mixed, at 250 DEG C, after dissolution 3 hours,
Potassium bifluoride 100kg, graphite powder 100kg mixing, in 150 DEG C of dry 3 hours obtained catalyst 5 is added.
Perfluorinated sulfonic resin model NR50 used in embodiment 1-5, buys, average grain diameter from Lancaster chemical company
0.9mm, acid amount 0.89mmol/g.
The preparation of 6 Dichloromonofluoromethane of embodiment
In the pipeline reactor for having been charged into catalyst 1, by feeding intake for chloroform 119.5kg/h and hydrogen fluoride 20kg/h
Amount is preheating to 60 DEG C or so in preheater respectively, is pressed into reactor.Reaction temperature is in 250 DEG C of temperature, and reaction pressure is in 1kg/
cm2It is reacted under absolute pressure, after reaction, material is evaporated to be separated into condensation separation tower, separates Dichloromonofluoromethane product
102kg/h, conversion ratio 99%, purity 99%.
The preparation of 7 Dichloromonofluoromethane of embodiment
In the pipeline reactor for having been charged into catalyst 2, by feeding intake for chloroform 119.5kg/h and hydrogen fluoride 60kg/h
Amount is preheating to 60 DEG C or so in preheater respectively, is pressed into reactor.In reaction temperature in 250 DEG C of temperature, reaction pressure exists
1kg/cm2It is reacted under absolute pressure, after reaction, material is evaporated to be separated into condensation separation tower, separates Dichloromonofluoromethane
Product 102kg/h, conversion ratio 99%, purity 99%.
The preparation of 8 Dichloromonofluoromethane of embodiment
In the pipeline reactor for having been charged into catalyst 3, by feeding intake for chloroform 119.5kg/h and hydrogen fluoride 40kg/h
Amount is preheating to 60 DEG C or so in preheater respectively, is pressed into reactor.In reaction temperature in 350 DEG C of temperature, reaction pressure exists
1kg/cm2It is reacted under absolute pressure, after reaction, material is evaporated to be separated into condensation separation tower, separates Dichloromonofluoromethane
Product 102kg/h, conversion ratio 99%, purity 99%.
The preparation of 9 Dichloromonofluoromethane of embodiment
In the pipeline reactor for having been charged into catalyst 4, by feeding intake for chloroform 119.5kg/h and hydrogen fluoride 30kg/h
Amount is preheating to 60 DEG C or so in preheater respectively, is pressed into reactor.In reaction temperature in 300 DEG C of temperature, reaction pressure exists
1kg/cm2It is reacted under absolute pressure, after reaction, material is evaporated to be separated into condensation separation tower, separates Dichloromonofluoromethane
Product 102kg/h, conversion ratio 99%, purity 99%.
The preparation of 10 Dichloromonofluoromethane of embodiment
In the pipeline reactor for having been charged into catalyst 5, by feeding intake for chloroform 119.5kg/h and hydrogen fluoride 50kg/h
Amount is preheating to 60 DEG C or so in preheater respectively, is pressed into reactor.In reaction temperature in 250 DEG C of temperature, reaction pressure exists
1kg/cm2It is reacted under absolute pressure, after reaction, material is evaporated to be separated into condensation separation tower, separates Dichloromonofluoromethane
Product 102kg/h, conversion ratio 99%, purity 99%.
Claims (6)
1. a kind of perfluorinated sulfonic resin catalyst, it is characterised in that: the catalyst includes perfluorinated sulfonic resin and carrier, the load
Body main carrier and secondary carrier, the main carrier are the bifluoride of alkali or alkaline earth metal, and the pair carrier is active carbon, stone
One or more of ink powder or land plaster；The weight ratio of the perfluorinated sulfonic resin, main carrier and secondary carrier be 1:1~
3:1~3.
2. a kind of preparation method of perfluorinated sulfonic resin catalyst as described in claim 1, it is characterised in that: by first by perfluor
Sulfonate resin is dissolved in water and Isopropanol Solvent, and then perfluorinated sulfonic resin is made and urges with main carrier, secondary carrier combination drying
Agent.
3. the preparation method of perfluorinated sulfonic resin catalyst according to claim 2, it is characterised in that: the perfluorinated sulfonic acid tree
The weight ratio of the component of rouge, water and Isopropanol Solvent is 1:0.1~1:1~1.5, and solution temperature is 200~300 DEG C, when dissolution
Between be 1~5 hour.
4. the preparation method of perfluorinated sulfonic resin catalyst according to claim 2, it is characterised in that: drying temperature 150
~200 DEG C, drying time is 1~3 hour.
5. a kind of perfluorinated sulfonic resin catalyst as described in claim 1 or according to claim 2-4 any one claim
Resulting perfluorinated sulfonic resin catalyst is preparing the application in Dichloromonofluoromethane.
6. applying according to claim 5, it is characterised in that: perfluorinated sulfonic resin catalyst is put into pipeline reactor,
Chloroform and hydrogen fluoride after preheated carried out at 250~350 DEG C continuity react be made Dichloromonofluoromethane, described three
The molar ratio of chloromethanes and hydrogen fluoride is 1:1~3.
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| CN201910316238.8A CN109939734B (en) | 2019-04-19 | 2019-04-19 | Perfluorosulfonic acid resin catalyst, preparation method and application in preparation of dichlorofluoromethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746265A (en) * | 2019-10-09 | 2020-02-04 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
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| JPS52156840A (en) * | 1976-06-23 | 1977-12-27 | Roussel Uclaf | Sulfonic acid esters of optically active allethrolone* process for manufacture thereof and use thereof to inversion of allethrolone at asymmetric center |
| CN102527414A (en) * | 2011-12-28 | 2012-07-04 | 临海市利民化工有限公司 | Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application |
| CN108863710A (en) * | 2018-06-20 | 2018-11-23 | 临海市利民化工有限公司 | A kind of preparation method of tetrafluoromethane |
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2019
- 2019-04-19 CN CN201910316238.8A patent/CN109939734B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156840A (en) * | 1976-06-23 | 1977-12-27 | Roussel Uclaf | Sulfonic acid esters of optically active allethrolone* process for manufacture thereof and use thereof to inversion of allethrolone at asymmetric center |
| CN102527414A (en) * | 2011-12-28 | 2012-07-04 | 临海市利民化工有限公司 | Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application |
| CN102527414B (en) * | 2011-12-28 | 2013-01-02 | 临海市利民化工有限公司 | Fluorination catalyst for preparing difluoromethane or monochlorodifluoromethane, preparation method and application |
| CN108863710A (en) * | 2018-06-20 | 2018-11-23 | 临海市利民化工有限公司 | A kind of preparation method of tetrafluoromethane |
| CN108863710B (en) * | 2018-06-20 | 2021-03-19 | 临海市利民化工有限公司 | Preparation method of tetrafluoromethane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746265A (en) * | 2019-10-09 | 2020-02-04 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
| CN110746265B (en) * | 2019-10-09 | 2021-02-26 | 浙江大学 | Method for continuously producing fluorinated alkane in pipeline manner by liquid phase method |
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